Substantially anhydrous and/or anhydrous chromium(III) halide complexes (e.g., CrCl3(THF)3) are useful materials for producing coordination and organometallic chromium compounds. Substantially anhydrous and/or anhydrous chromium complexes of this type generally are expensive to produce and few convenient synthetic techniques are available. For example, current methods can require either the separate formation of the substantially anhydrous and/or anhydrous CrCl3 from CrCl3 hydrate, or employ dehydrating agents that produce acid as a result of their dehydrating action. Such methods typically require heating and/or vacuum, and the presence of acid. Chromium(III) halide complexes produced via these methods can contain impurities or by-products which can be detrimental to preparing coordination and organometallic chromium compounds and/or catalyst systems containing the prepared coordination and organometallic chromium compounds. Therefore, more convenient and simpler methods to form substantially anhydrous and/or anhydrous chromium(III) halide complexes such as CrCl3(THF)3 are needed. Moreover, methods to form substantially anhydrous and/or anhydrous chromium(III) halide complexes such as CrCl3(THF)3 that do not require substantial heating under vacuum or produce acid as a result of the dehydration process would be desirable.